Novel spectral and electrochemical characteristics of triphenylamine-bound zinc porphyrins and their intramolecular energy and electron transfer

Porphine bearing triphenylamine (TPA) pendant groups and their zinc complexes, zinc meso-tetra-p-(di-p-phenylamino)phenylporphyrin (ZnTDPAPP) and zinc meso-tetra-p-(di-p-tolylamino)phenylporphyrin (ZnTDTAPP) are synthesized and their spectral and electrochemical characteristics are studied. Zinc meso-tetraphenylporphyrin (ZnTPP) and zinc meso-tetra-p-aminophenylporphyrin (ZnTAPP) are also used as reference complexes. The B and Q bands of ZnTDPAPP and ZnTDTAPP are located at higher wavelengths and the bandwidths become broader compared with those of ZnTPP and ZnTAPP, indicating the peripheral TPA affects the electronic configuration of zinc porphyrins. Upon excitation in CH2Cl2 at room temperature, the compounds exhibit intramolecular singlet energy transfer from the TPA to the porphyrin core, and emission from the porphyrins are observed. Both ZnTDPAPP and ZnTDTAPP are easier to be oxidized and harder to be reduced than ZnTPP, in agreement with the strong electron-donating effect of the TPA groups. Extra waves corresponding to the oxidation of TPA substituents are also observed. The cation radical ZnTDTAPP+* exhibits an absorption spectrum very different from the typical spectra for porphyrin cation radicals. The NIR absorption band at 1296 nm indicates the electron transfer occurs intramolecularly. The above results evince the ability of TPA to modulate the electronic structure of zinc porphyrins.     

Preparation, electrochemical and spectral properties of N-methyl-pyridylethynyl nickel porphyrins

A series of nickel N-methyl-pyridylethynylporphines were synthesized and their electrochemical and absorption properties were studied. UV-visible spectra of these complexes show that the absorption red-shifts of the nickel porphyrins are as significant as the zinc analogues. Although the reduction potential shifts caused by the electron-withdrawing substituents are not as large as the zinc complexes, the first reduction potentials of the nickel porphyrins are more positive than those of the zinc counterparts. In addition, the redox behaviors of these nickel porphyrins are similar to those of the zinc analogues.     

Energy transfer in zinc porphyrin-phthalocyanine heterotrimer and heterononamer studied by fluorescence resonance energy transfer (FRET)

Two or eight zinc triphenyl porphyrins were conjugated with Zn-phthalocyanine or H2-phthalocyanine to form ZnPc-(ZnTPP)2, ZnPc-(ZnTPP)8, H2Pc-(ZnTPP)2 and H2Pc-(ZnTPP)8. Energy transfers from the porphyrin moiety to phthalocyanine part were quantitatively studied with the modality of fluorescence resonance energy transfer (FRET). By measuring the fluorescence increment from the phthalocyanine moiety and the decrease from porphyrin part under selective excitation at the B band of the porphyrin part in those conjugated compounds and their equimolar mixture of compositions, energy transfer efficiencies were estimated to be 90% for H2Pc-(ZnTPP)8 and ZnPc-(ZnTPP)8, and 60%, 30% for ZnPc-(ZnTPP)2 and H2Pc-(ZnTPP)2, respectively.     

Preparation, electrochemical and spectral properties of N-methylated pyridylethynyl porphyrins

A new series of electron-deficient porphyrins were prepared by attaching one or two N-methylated 2-, 3- or 4-pyridylethynyl groups to the 10,20-meso positions of (5,15-biphenylporphinato)zinc(II). Electrochemical studies showed significant changes in the reduction potentials of these porphyrins, and N-methyl-2-pyridylethyne is the strongest electron-withdrawing substituent in the series. UV-visible spectra demonstrated largely red-shifted absorptions, and N-methyl-4-pyridylethyne has the greatest impact to the porphyrin absorptions. Electrochemical, UV-visible and EPR results concluded that porphyrins Zn2 and Zn6 reversibly undergo two one-electron porphyrin-ring reductions to their anion radicals then dianions. The first reductions of porphyrins Zn1, Zn3, Zn4 and Zn5 were irreversible one-electron transfer processes. The instability of these reduction products was suggested to result from the eletrophilic attacks at the substituents.     

Electrochemical studies of corrphycenes and metallocorrphycenes

Corrphycene 3 (Cn) is a structural isomer of porphyrin 1 that was synthesized for the first time 5 years ago. This paper reports on the redox properties of free-base octaethylcorrphycene H2OECn and 16 metal complexes derived therefrom. In CH2Cl2 solution, the free base and the metallo(II) octaethylcorrphycenes, M(II)OECn, typically undergo four distinct one-electron redox steps involving the tetrapyrrolic macrocycle, of which two are reduction steps and two are oxidations. One exception to this general pattern is displayed by the Co(II)OECn complex. In this instance, the first one-electron reduction is metal-centered and produces Co(I)OECn. A comparison of the redox potentials of corrphycenes with those of porphyrins and porphycenes indicates that the first reduction potentials of the free base and of the metallo-octaethylcorrphycenes are between those of the porphycenes-the easiest to reduce molecules in this set of isomeric tetrapyrrolic systems-and those of the porphyrins. The oxidation potentials of corrphycenes and porphyrins are found to be quite similar. On the other hand, porphycenes are oxidized at less positive potentials. The redox gap deltaE1/2 = E1/2Ox1 - E1/2Red1 is equal to 2.15 +/- 0.08 V for the free base corrphycene and the various metallocorrphycenes that were subjected to study. This redox gap is not much different from that observed in porphyrins (deltaE1/2 = 2.25 +/- 0.1 V), whereas if differs significantly from that observed in porphycenes (deltaE1/2 = 1.85 +/- 0.15 V). The sequence of these deltaE1/2 values parallels the lowest energy absorption maxima observed in the UV-vis spectra of these three isomers.     

Surface-enhanced Raman scattering at the silver electrode/ionic liquid (BMIPF6) interface

This is the first report of in situ SER spectra of chemical species adsorbed on a Ag/room temperature ionic liquid (RTIL) interface. We have investigated the dependence of the SERS intensity of the RTIL derived from 1-n-butyl-3-methylimidazolium hexafluorophosfate (BMIPF6) adsorbed on a silver electrode. It has been shown that the BMI+ adsorbs on the silver electrode for potentials more negative than -0.4 V vs a Pt quasireference electrode (PQRE). In the -0.4 to -1.0 V potential range the SER spectra are similar to the Raman spectrum of the RTIL BMIPF6. At potentials more negative than -1.0 V some imidazolium ring vibrational modes and N-CH3 vibrations are enhanced, suggesting that the imidazolium ring is parallel to the surface and for potentials <-2.8 V the BMI+ is reduced to the BMI carbene. The potential dependence of the SERS intensities of Py adsorbed on a silver electrode in BMIPF6 has also been investigated. The results have shown that at potentials less negative than -0.8 V (vs PQRE) Py adsorbs at an end-on configuration forming an Ag-N bond. In the -0.9 to -1.4 V potential range Py molecules lie flat on the electrode surface and at potentials <-1.4 V Py is replaced by the BMI+. The electrochemical and SERS results have shown that Py has the effect of changing the oxidation of silver in that medium as well as the reduction of BMI+ to the BMI carbene. In the presence of Py the BMI+ reduction is observed at potentials near -2.4 V. The Ag electrode has presented SERS activity from 0.0 to -3.0 V.     

Zinc(II) porphyrins at the air-water interface as studied by polarized total-reflection X-ray absorption fine structure

The polarized total-reflection X-ray absorption fine structure method was applied to characterize zinc porphyrins at the air-water interface. The X-ray absorption near edge structure exhibited a significant difference depending on the polarization of the X-ray. A shoulder peak of the Zn K-edge corresponding to the 1s-4p(z) transition for a square planar metal complex without axial coordination(s) was observed at 9662 eV, which indicates that the axial coordination sites of zinc porphyrin molecules examined are not fully hydrated at the air-water interface. The molecular orientation of zinc porphyrins was determined by analyzing the polarization dependence of the transition peak intensity. The meso-substituted porphyrin derivative 5,10,15,20-tetraphenylporphyrinatozinc(II) (ZnTPP) orients rather parallel to the solution surface. In contrast to ZnTPP, the zinc(II) protoporphyrin IX (ZnPP) with hydrophilic carboxyl groups at one side of the molecule stands up with respect to the solution surface, and the average tilting angle of the porphyrin plane to the surface was evaluated to be between 57 degrees and 43 degrees. In addition, the axial coordination of ZnPP is modified depending on the surface concentration, in which the axial hydration to the zinc center is effectively inhibited in the compressed surface layer.     

Synthesis and electronic properties of regioisomerically pure oxochlorins

We describe a two-step conversion of C-alkylated zinc chlorins to zinc oxochlorins wherein the keto group is located in the reduced ring (17-position) of the macrocycle. The transformation proceeds by hydroxylation upon exposure to alumina followed by dehydrogenation with DDQ. The reactions are compatible with ethyne, iodo, ester, trimethylsilyl, and pentafluorophenyl groups. A route to a spirohexyl-substituted chlorin/oxochlorin has also been developed. Representative chlorins and oxochlorins were characterized by static and time-resolved absorption spectroscopy and fluorescence spectroscopy, resonance Raman spectroscopy, and electrochemistry. The fluorescence quantum yields of the zinc oxochlorins (Phi(f) = 0.030-0.047) or free base (Fb) oxochlorins (Phi(f) = 0.13-0.16) are comparable to those of zinc tetraphenylporphyrin (ZnTPP) or free base tetraphenylporphyrin (FbTPP), respectively. The excited-state lifetimes of the zinc oxochlorins (tau = 0.5-0.7 ns) are on average 4-fold lower than that of ZnTPP, and the lifetimes of the Fb oxochlorins (tau = 7.4-8.9 ns) are approximately 40% shorter than that of FbTPP. Time-resolved absorption spectroscopy of a zinc oxochlorin indicates the yield of intersystem crossing is >70%. Resonance Raman spectroscopy of copper oxochlorins show strong resonance enhancement of the keto group upon Soret excitation but not with Q(y)()-band excitation, which is attributed to the location of the keto group in the reduced ring (rather than in the isocyclic ring as occurs in chlorophylls). The one-electron oxidation potential of the zinc oxochlorins is shifted to more positive potentials by approximately 240 mV compared with that of the zinc chlorin. Collectively, the fluorescence yields, excited-state lifetimes, oxidation potentials, and various spectral characteristics of the chlorin and oxochlorin building blocks provide the foundation for studies of photochemical processes in larger architectures based on these chromophores.     

Zinc(II) tetraarylporphyrins anchored to TiO2, ZnO, and ZrO2 nanoparticle films through rigid-rod linkers

A series of six Zn(II) tetraphenylporphyrins (ZnTPP), with a phenyl (P) or oligophenyleneethynylene (OPE = (PE) n ) rigid-rod bridge varying in length (9-30 A) and terminated with an isophthalic acid (Ipa) anchoring unit, were prepared as model dyes for the study of sensitization processes on metal oxide semiconductor nanoparticle surfaces (MO(n) = TiO(2), ZnO, and insulating ZrO(2)). The dyes were designed such that the electronic properties of the central porphyrin chromophore remained consistent throughout the series, with the rigid-rod anchoring unit allowing each porphyrin unit to be located at a fixed distance from the metal oxide nanoparticle surface. Electronic communication between the porphyrin and the rigid-rod unit was not desired. Rigid-rod porphyrins ZnTPP-Ipa, ZnTPP-P-Ipa, ZnTPP-PE-Ipa, ZnTPP-(PE)(2)-Ipa, ZnTPP-(PE)(3)-Ipa, and ZnTMP-Ipa (with mesityl substituents on the porphyrin ring) were synthesized using combinations of mixed aldehyde condensations and Pd-catalyzed cross-coupling reactions. Their properties, in solution and bound, were compared with that of Zn(II) 5,10,15,20-tetra(4-carboxyphenyl)porphyrin ( p-ZnTCPP) as the reference compound. Solution UV-vis and steady-state fluorescence spectra for all six rigid-rod-Ipa porphyrins were almost identical to each other and to that of p-ZnTCPP. Cyclic voltammetry and differential pulse voltammetry scans of the methyl ester derivatives of the six rigid-rod-Ipa porphyrins, recorded in dichloromethane/electrolyte, exhibited redox behavior typical of ZnTPP porphyrins, with the first oxidation in the range +0.99 to 1.09 V vs NHE. All six rigid-rod-Ipa porphyrins and p-ZnTCPP were bound to metal oxide (MO(n) = TiO(2), ZnO, and insulating ZrO(2)) nanoparticle films. The Fourier transform infrared attenuated total reflectance spectra of all compounds bound to MO n films showed a broad band at 1553-1560 cm(-1) assigned to the v(CO(2)(-)) asymmetric stretching mode. Splitting of the Soret band into two bands at 411 and 423 nm in the UV-vis spectra of the bound compounds, and broadening and convergence of both fluorescence emission bands in the fluorescence spectra of the porphyrins bound to insulating ZrO(2) were also observed. Such changes were less evident for ZnTMP-Ipa, which has mesityl substituents on the porphyrin ring to prevent aggregation. Steady-state fluorescence emission of rigid-rod-Ipa porphyrins bound to TiO(2) and ZnO through the longest bridges (>14 A) showed residual fluorescence emission, while fluorescence quenching was observed for the shortest compounds.     

Photoinduced hydrogen production using a multilayered molecular assembly composed of zinc tetraphenylporphine and Nafion® membrane

A photoinduced proton reduction to produce H₂ was found to take place in the system using zinc tetraphenylporphine (ZnTPP) incorporated into a Nafion® membrane coated on a platinum electrode (denoted as Pt/Nf[ZnTPP]). When visible light (λ > 390 nm) was irradiated on the Pt/Nf[ZnTPP] system, a photocurrent was generated under applied potentials below −0.10 (v. Ag/AgCl). The action spectrum for the photocurrent agreed with the absorption spectrum of the Nf[ZnTPP] membrane, showing that the present photochemical process is induced on light absorption by the ZnTPP. By measuring the emission decay of ZnTPP under the photoelectrochemical conditions, it was exhibited that the emission from the singlet excited ZnTPP is quenched by the cathodic potentials. The amount of the H₂ produced increased with the cathodic potentials. These results indicated that, in the photochemical primary process, a reductive quenching takes place by electron injection from the Pt electrode to the singlet excited ZnTPP forming ZnTPP^.–, subsequently leading to the H₂ formation by a bimolecular catalysis of the ZnTPP. Copyright © 2000 John Wiley & Sons, Ltd.     

Spectroscopy of free-base N-confused tetraphenylporphyrin radical anion and radical cation

The radical anions and radical cations of the two tautomers (1e and 1i) of 5,10,15,20-tetraphenyl N-confused free-base porphyrin have been studied using a combination of cyclic voltammetry, steady state absorption spectroscopy, and computational chemistry. N-Confused porphyrins (NCPs), alternatively called 2-aza-21-carba-5,10,15,20-tetraphenylporphyrins or inverted porphyrins, are of great interest for their potential as building blocks in assemblies designed for artificial photosynthesis, and understanding the absorption spectra of the corresponding radical ions is paramount to future studies in multicomponent arrays where electron-transfer reactions are involved. NCP 1e was shown to oxidize at a potential of E(ox) 0.65 V vs Fc(+)|Fc in DMF and reduce at E(red) -1.42 V, while the corresponding values for 1i in toluene were E(ox) 0.60 V and E(red) -1.64 V. The geometries of these radical ions were computed at the B3LYP/6-31+G(d)//B3LYP/6-31G(d) level in the gas phase and in solution using the polarizable continuum model (PCM). From these structures and that of H(2)TPP and its corresponding radical ions, the computed redox potentials for 1e and 1i were calculated using the Born-Haber cycle. While the computed reduction potentials and electron affinities were in excellent agreement with the experimental reduction potentials, the calculated oxidation potentials displayed a somewhat less ideal relationship with experiment. The absorption spectra of the four radical ions were also measured experimentally, with radical cations 1e(?+) and 1i(?+) displaying significant changes in the Soret and Q-band regions as well as new low energy absorption bands in the near-IR region. The changes in the absorption spectra of radical anions 1e(?-) and 1i(?-) were not as dramatic, with the changes occurring only in the Soret and Q-band regions. These results were favorably modeled using time-dependent density functional calculations at the TD-B3LYP/6-31+G(d)//B3LYP/6-31G(d) level. These results were also compared to the existing data of free base tetraphenylporphyrin and free base tetraphenylchlorin.     

Synthesis, characterization, and electrochemical studies of beta,beta'-fused metallocenoporphyrins

Beta,beta'-Fused monoruthenocenylporphyrins, Cp*Ru(III)[1,2-[M(II)-5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)-porphyrinato]-3-methyl-cyclopentadienide] (M = Ni (20), Cu (21), Zn (22)), and bisferrocenoporphyrins, Fe(II) bis[1,2-[M(II)-5,10,15,20-tetraphenylporphyrinato]-3-methyl-cyclopentadienide] (M = Ni (24), Cu (25), Zn (26)), were synthesized and characterized. A novel synthetic approach to beta,beta'-fused porphyrins through Pd(0)-catalyzed [3 + 2] cycloaddition was implemented in this work. UV-vis spectra of these compounds show largely broadened and red-shifted bands (relative to their precursors) indicating potential electronic communication between the attached organometallic moiety and the porphyrin core. The electrochemistry of these molecules suggests significant electronic interactions between the metallocene and metalloporphyrin in molecules 20 and 24. The crystal structure of the bisferrocenoporphyrin 26, Fe(II) bis[1,2-[Zn(II)-5,10,15,20-tetraphenylporphyrinato]-3-methyl-cyclopentadienide], was determined: [Cp2Fe[ZnTPP(THF)]2][Cp2Fe[ZnTPP(THF)ZnTPP(MeOH)]].3MeOH.6THF, M = 3804.35, monoclinic, space group P21/c, a = 33.327(5) A, b = 19.145(3) A, c = 29.603(5) A, beta = 106.309(2) degrees , V = 18128(5) A3, Z = 4. In this molecule, one porphyrin ring is rotated by about 72 degrees with respect to the other in the 5-fold axis of the Cp ring.     

Highly conjugated multiporphyrins: synthesis, spectroscopic and electrochemical properties

A series of meso-to-meso ethynyl-bridged multiporphyrin arrays have been synthesized using Sonogoshira palladium-catalyzed cross-coupling reactions involving the appropriate ethynylporphyrin and iodoporphyrin precursors. The absorption spectra of these multiporphyrins show splitting of the Soret bands and significant red shifts of the Q bands as compared to the combination of the corresponding components. These conjugated multiporphyrins also show red shifts in their emission spectra as the pi-conjugation is expanded. In the electrochemical measurements, the porphyrins dimer 7 shows two 1 - e- oxidations at E(1/2) = +0.63 and +0.76 V for the first electron abstraction from the two porphyrin rings, indicating electronic communication between the two porphyrin units. The porphyrin trimer 4 exhibits the first and second 1 - e- oxidations at E(1/2) = +0.68 and +0.77 V, respectively, which correspond to the two outer porphyrins. The cyclic voltammogram of pentamer 5 shows two overlapping 1 - e- couples at E(1/2) = +0.56 and +0.66 V, and one 2 - e- couple at E(1/2) = +0.86 V, for the four outer porphyrin units. These results demonstrate that in the porphyrin trimer and pentamer the individual peripheral porphyrin units are electrochemically coupled via a central porphyrin core. The UV-Vis-NIR spectra of the oxidized species of these multiporphyrins exhibit a broad intervalence charge transfer (IVCT) band in the region from 1200 to 3000 nm. The present work shows that a central porphyrin unit appended with ethynyl bridges affords strong electronic interactions between the peripheral porphyrin rings over a distance of about 15 A.     

Dynamics of closure of zinc bis-porphyrin molecular tweezers with copper(II) ions and electron transfer

Zinc bis-porphyrin molecular tweezers composed of a N(4) spacer bound through pyridyl units to the meso position of porphyrins were synthesized, and the tweezers are closed by the coordination of a copper(II) ion inside the spacer ligand. The effect of the π-π interaction between the porphyrin rings in the closed conformation on the absorption spectra of multi-electron oxidized species and the reduction potentials were clarified by chemical and electrochemical oxidation of the closed form of the zinc bis-porphyrin molecular tweezers in comparison with the open form without copper(II) ion and the corresponding porphyrin monomer. The shifts in redox potentials and absorption spectrum of the porphyrin dication indicate a strong electronic interaction between the two oxidized porphyrins in the closed form, whereas there is little interaction between them in the neutral form. The dynamics of copper(II) ion coordination and subsequent electron transfer was examined by using a stopped-flow UV/Vis spectroscopic technique. It was confirmed that coordination of copper(II) occurs prior to electron-transfer oxidation of the closed form of the zinc bis-porphyrin molecular tweezers.     

Investigation of tightly coupled porphyrin arrays comprised of identical monomers for multibit information storage

Our prior designs for molecular-based information storage devices have employed multiple redox-active units organized in weakly coupled, covalently linked arrays. To explore a simpler design, we report here the synthesis of porphyrin arrays where porphyrins with identical oxidation potentials are directly linked to one another instead of joined via a molecular linker. Oxidative coupling with AgPF(6) of zinc(II)-5,15-bis(4-tert-butylphenyl)-10-phenylporphyrin, obtained by a rational synthesis, afforded the expected dimer joined by a meso-meso linkage and an unexpected trimer joined by meso-meso linkages. For attachment to an electroactive surface we synthesized a meso-linked porphyrin dimer with a thiol-linker in one of the meso positions. The S-acetyl protecting group was used to avoid handling free thiol groups. Coupling of zinc(II)-5,10,15-tris(3, 5-di-tert-butylphenyl)porphyrin ("upper half") and zinc(II)-5-[4-(S-acetylthio)phenyl]-10,20-bis(3, 5-di-tert-butylphenyl)porphyrin ("lower half") afforded three different meso-linked dimers with the desired dimer as the main product. Electrochemical examination of the meso-linked dimer in solution shows that the first two oxidation potentials of the array differ by approximately 0.15 V and straddle the value exhibited by the monomeric constituents. The third and fourth oxidation potentials of the array are also split although to a lesser extent ( approximately 0.08 V) than the first and second. For the meso-linked trimer, the first three oxidation waves are also split; however, these waves are severely overlapped. The electrochemical behavior of the dimers and trimer is indicative of strong electronic interactions among the porphyrins. The thiol-derivatized meso-linked dimers form self-assembled monolayers (SAMs) on gold via in situ cleavage of the S-acetylthio protecting group. The porphyrin SAM exhibits four well-resolved oxidation waves. Regardless, the meso-meso linkage is relatively unstable upon formation of the pi-cation radical(s). This characteristic indicates that the structural motif is of limited utility for molecular information storage elements.     

Fluorinated photosensitizers: synthesis, photophysical, electrochemical, intracellular localization, in vitro photosensitizing efficacy and determination of tumor-uptake by F in vivo NMR spectroscopy

For in vivo NMR studies, starting from pyrroles, a series of fluorinated porphyrins were synthesized by following the MacDonald reaction conditions. Upon reaction with osmium tetroxide, a fluorinated porphyrin containing four trifluoromethyl groups (12 fluorine units) was converted into the related chlorin and bacteriochlorin which exhibited long-wavelength absorptions at 652 and 720 nm, respectively. All compounds produced good singlet oxygen production efficiency. A comparative study of nine porphyrins with and without fluorine substituents indicated no adverse effects of the presence of fluorinated groups in the photophysical properties of the porphyrins, chlorins or bacteriochlorins. The first and second one-electron reduction potentials (vs SCE) of the investigated compounds range between −1.29 and −1.49 V and between −1.66 and −1.84 V in PhCN containing 0.1 M TBAP. UV-visible spectroelectrochemical data suggested the formation of π-anion and π-cation radicals upon the first reduction and first oxidation. The in vivo ¹⁹F MR study of a representative fluorine labeled compound with twelve equivalent fluorines confirmed the presence of the fluorine labeled sensitizer in mouse (C3H/HeJ) implanted with RIF tumors on mouse foot dorsum by inoculating 2×10⁵ cells (the studies were repeated on four tumored mice to confirm the feasibility and reproducibility). All fluorinated compounds were found to be quite effective in vitro. In a comparative intracellular localization study with Rhodamine-123 in RIF tumor cells, the most soluble porphyrin containing two propionic ester side chains was found to localize in mitochondria as well as the related chlorin and bacteriochlorin.     

四苯基卟啉锌J-聚集体的光谱与晶体结构分析

四苯基卟啉锌在完全无水的乙氰中发生自聚现象, 聚集体的形成可以通过稳态光谱来证实. 吸收光谱和荧光发射光谱的红移表明四苯基卟啉锌的聚集体是卟啉之间以头对头的方式排列, 即J-聚集体. 进一步研究表明聚集体的形成还依赖于溶剂. 光谱和激发态寿命的测定结果表明聚集体的辐射跃迁速率比单体快两倍, 这表明形成的J-聚集体存在超辐射. 四苯基卟啉锌的晶体呈现出杆状的结构. 通过X射线的结构分析, 提出了一个四苯基卟啉锌J-聚集体的结构模型. 四苯基卟啉锌中的一个苯基和相邻的四苯基卟啉锌中的吡咯垂直并通过C—H…π键相互作用. 最后讨论了乙氰配位后对四苯基卟啉锌中Zn—N键的影响.     

Ultrafast intersystem crossing and spin dynamics of zinc meso-tetraphenylporphyrin covalently bound to stable radicals

tert-Butylphenylnitroxide (BPNO(?)) and α,γ-bisdiphenylene-β-phenylallyl (BDPA(?)) stable radicals are each attached to zinc meso-tetraphenylporphyrin (ZnTPP) at a fixed distance using one of the ZnTPP phenyl groups. BPNO(?) and BDPA(?) are oriented para (1 and 3, respectively) or meta (2 and 4, respectively) relative to the porphyrin macrocycle. Following photoexcitation of 1-4, transient optical absorption spectroscopy is used to observe excited state quenching of (1)*ZnTPP by the radicals and time-resolved electron paramagnetic resonance (TREPR) spectroscopy is used to monitor the spin dynamics of the paramagnetic product states. The presence of BPNO(?) or BDPA(?) accelerates the intersystem crossing rate of (1)*ZnTPP about 10- to 500-fold in 1-4 depending on the structure compared to that of (1)*ZnTPP itself. In addition, the lifetime of (3)*ZnTPP in 1 is shorter than that of (3)*ZnTPP itself as a result of enhanced intersystem crossing (EISC) from (3)*ZnTPP to the ground state. The TREPR spectra of the three unpaired spins produced within 1 and 2 show spin-polarized excited doublet (D(1)) and quartet (Q) states and subsequent formation of a spin-polarized ground state radical (D(0)). All three signals are absorptive for 1 and emissive for 2. Polarization inversion of the Q state is observed on a tens of nanoseconds time scale in 2, while no polarization inversion is observed for 1. The lack of polarization inversion in 1 is attributed to the short lifetime of the doublet-quartet manifold as a result of the very large exchange interaction. The TREPR spectra of 3 and 4 show ground state radical polarization at X-band (9.5 GHz) at room temperature, but not at 85 K, and similarly no polarization is observed at W-band (94 GHz). No evidence of excited doublet or quartet states is observed, indicating that the exchange interaction is both weak and temperature dependent. These results show that although ultrafast EISC produces (3)*ZnTPP within 1-4, the magnitude of the exchange interactions between the three relevant spins in the resulting (3)*ZnTPP-BPNO(?) and (3)*ZnTPP-BDPA(?) systems dramatically alters their spin dynamics.     

The breakdown of β-alumina at positive and negative potentials

The breakdown of β^″-alumina at blocking electrodes, over a range of potentials from ?3 V to +8 V relative to the I₂/NaI couple, has been studied. The dependence of current and of interfacial capacitance on potential indicates that oxygen reduction occurs at a less negative potential (ca. ?1.8 V) than sodium deposition (ca. ?2.9 V). No evidence of anodic decomposition could be found over the entire potential range, suggesting that there is a substantial kinetic barrier to formation of oxygen gas from the oxygen anions in the lattice.     

COMPARTMENTALIZATION OF ZINQII) TETRAPHENYLPORPHYRIN IN A HYDROPHOBIC MICRODOMAIN OF AN AMPHIPHILIC POLYELECTROLYTE: A PHYSICOCHEMICAL MODEL OF BIOLOGICAL METALLOPORPHYRIN SYSTEMS

Abstract— Small mole fractions of zinc(II) tetraphenylporphyrin (ZnTPP) moieties were covalently incorporated into amphiphilic polysulfonates having bulky hydrophobic groups such as lauryl, cyclododecyl, and (2-naphthyi)methyl (Np) groups in their side chains. The ZnTPP moieties are "compartmentalized" in the hydrophobic domains of these amphiphilic polyelectrolytes in aqueous solution. For comparison, the ZnTPP moieties were covalently incorporated into a polysulfonate without hydrophobic groups. The ZnTPP moieties in this reference polymer are exposed to water in aqueous solution. The compartmentalized ZnTPP systems in aqueous fluid solution emitted phosphorescence and thermally activated delayed fluorescence at room temperature. This is due to an extremely long-lived triplet excited state in the compartmentalized systems at room temperature in aqueous solution, e.g. 19 ms for ZnTPP compartmentalized in Np domains, compared with 3 ms for ZnTPP in the reference polymer. These remarkable compart-mentalization effects may be attributed to a restriction of motional freedom of the ZnTPP moiety isolated in a rigid and hydrophobic microenvironment provided by the amphiphilic polyelectrolytes in aqueous solution.